EP0967956A1 - Teilcheförmiges hydrogelmaterial - Google Patents
Teilcheförmiges hydrogelmaterialInfo
- Publication number
- EP0967956A1 EP0967956A1 EP98907070A EP98907070A EP0967956A1 EP 0967956 A1 EP0967956 A1 EP 0967956A1 EP 98907070 A EP98907070 A EP 98907070A EP 98907070 A EP98907070 A EP 98907070A EP 0967956 A1 EP0967956 A1 EP 0967956A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- glass
- paste
- acid
- cement
- fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- A61K6/889—Polycarboxylate cements; Glass ionomer cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/28—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing organic polyacids, e.g. polycarboxylate cements, i.e. ionomeric systems
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00836—Uses not provided for elsewhere in C04B2111/00 for medical or dental applications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/80—Optical properties, e.g. transparency or reflexibility
Definitions
- PARTICULATE HYDROGEL MATERIAL This invention relates to a particulate hydrogel material usable in for example dental cement or light-curable paste formulations.
- a particulate material according to the present invention comprises a continuous matrix phase of fluoride-containing gel and a dispersed phase of non-fluoride silica gel, and which is the product of reacting to completion an acid-degradable glass with an acid polymer by an acid-base cement-forming reaction.
- Glass in this specification can include, according to the context, gelatinising minerals such as bentonite or other mixed metal oxides.
- the particulate material may be considered to be a glass-depleted polyalkenoate and/or polyphosphonate cement gel, that is, an acid-base reaction cement between a polyalkenoic acid or polyphosphonic acid and a glass (as a base), in which gel the glass is depleted compared with cements as normally formulated.
- the glass-depleted cement gels can be used in a number of distinct light cured dental materials, such as a liner, fissure sealant, bonding agent/adhesive and anterior restorative. They may also be incorporated in existing cement formulations as fluoride releasing agents, e.g. incorporation in non-resin based cements and also existing resin based cements.
- aluminosilicate glass is reacted with acid.
- the outer layer of each glass particle is depleted of metal ions and is degraded to a silica gel.
- the metal ions have been released by the action of the acid to migrate to the surrounding liquid phase, where they are initially soluble but then accumulate to cause gelation and become insoluble.
- the resulting cement thus has the form of dispersed particles each having an unreacted aluminosilicate glass core surrounded by a metal-depleted silica gel shell, the shell being about l A micron thick, the particles being dispersed in a gelated matrix of polyacid chains to which the metal ions which were released from the glass are bound.
- the shell attained this thickness of about l ⁇ micron during the period while the material surrounding it remained liquid and reactive. The shell ceases to thicken when the surrounding material has set.
- the unreacted aluminosilicate glass cores of the prior art are no longer present.
- the glass particles prior to reaction advantageously not exceeding 2 microns, preferably not exceeding V ⁇ microns and ideally not exceeding 1 micron, and preferably being spherical, the acid can release all the metal ions throughout the full depth of each particle before the system gels, leaving simply silica gel cores dispersed in a gelated matrix of polyacid chains to which the metal ions which were released from the glass are bound.
- the fluoride solution is one from which ammonia can evolve, such as ammonium hydrogen difluoride NH 4 .HF 2 , ammonium fluoride, ammonium heptafluorotantalate (V), ammonium hexafluorogermanate (IN), ammonium hexafluoroniobate, ammonium hexafluorophosphate, ammonium hexafluorosilicate, ammonium hexafluorotitanate (IV), ammonium tetrafluoroborate, ammonium trifluoroacetate or ammonium trifluoromethanesulfonate.
- ammonium hydrogen difluoride NH 4 .HF 2 ammonium fluoride, ammonium heptafluorotantalate (V), ammonium hexafluorogermanate (IN), ammonium hexafluoroniobate, ammonium hexafluorophosphate, ammonium he
- Low melting point for ammonium hydrogen difluoride it is 125C
- high acidity of the aqueous solution of these chemicals enhance their fluoride imparting action.
- the use of ammonium salts is preferable to employing HF, to avoid risks.
- the use of ammonium cations and fluoriferous anions will deposit F and no cations. Deposited cations will change the composition of the glasses, a complication avoided by the present invention.
- ammonium hydrogen difluoride or its analogues deactivates the surfaces of glasses by the crystallisation of calcium fluoride.
- glass ionomer cements glass polyalkenoate cements
- increases in working time with the addition of increased quantities of ammonium hydrogen difluoride are observed.
- the use of this ammonium salt on fluoride-free glass can even result in fluoride-containing non-setting glasses, as well as snap setting glasses.
- the former enables glass powders to be reacted with poly(acrylic acid) and tartaric acid in the presence of water to achieve neutralisation before gelation. Achieving neutralisation before gelation is a prerequisite to the formation of glass core-free cements.
- the snap-setting glasses resulting in cements that can set rapidly at the ends of their working times, within 20 seconds, may be used in glass-ionomer cements, which could rival command cure resin-based cements in their rapidity of set and low oral solubility.
- Fluoride (from the aforesaid fluoride solution) will substitute into the glass irrespective of particle size. However, if over- 1 -micron glasses are used as components of single paste resin systems, these systems will not be stable because the glass particles will continue reacting with water/acid during storage. Having said this, the F-containing glass and resulting cement could usefully be used as fluoride reservoir in carboxylate systems, even if they are less effective than the sub-micron glasses. Bentonite, for example, would not be reactive enough to participate in an acid-base reaction, but its reactivity can be improved by introducing fluoride as set forth above, typically by reacting the Al 2 O 3 to form A1F 3 .
- This method may be used on glass to be made into a particulate material as set forth above, whereby such material becomes suitable for use in a dental cement formulation as a fluoride release reservoir, and can be considered as a "reactive filler" compatible with most if not all dental material curing routes.
- the invention makes possible single-paste resin systems, and extends to a light-curable paste comprising a cross-linkable monomer, a light-activated initiator and a particulate material as set forth above.
- a light-curable paste comprising a cross-linkable monomer, a light-activated initiator and a particulate material as set forth above.
- Such paste may further comprise a zinc-containing glass, a polyalkenoic acid and optionally water so packed as to keep the pH below 4, and optionally contains Ba, Sr or other divalent glass-forming radio-opaque cation from the reacted glass.
- Another paste may further comprise an aqueous solution of an acid polymer capable of participating in a glass ionomer setting reaction.
- These two pastes may be presented in a two-paste cement pack, packed out of contact with each other (and preferably in opaque and/or air-tight packaging as appropriate) until the time of use.
- one or both pastes further comprise a non-zinc acid-degradable glass and/or a polymeric acid and/or water, such that neither paste reacts until it is unpacked and/or mixed with the other paste.
- the slurry was calcined in an oven over 24 hours via a progressive increase in temperature from 98°C to 250°C.
- the resulting off-white powder (5 parts) was mixed with 0.4 parts of dry poly(acrylic acid) and 0.15 parts tartaric acid to make 5.55 parts of a powder component.
- 8.33 parts of a liquid component were made from 4.90 parts of water, 2.45 parts of dry poly(acrylic acid) and 0.98 parts of tartaric acid.
- the 5.55 parts of the powder component were mixed with the 8.33 parts of the liquid component to form a cement.
- the cured cement gel was ground and passed through a 45 micron sieve.
- the sieved lot may be referred to as fluoridated glass-depleted cement, or ground cement, or in other terminology an ionomer gel.
- Example 1 was repeated, but using 2.158 g of ammonium hydrogen difluoride in step 1) instead of the 2.877 g.
- step 4 the slurry was heat-treated for 24 hours at 220°C.
- step 8 the oven was maintained at 100°C.
- Example 3
- Example 1 was repeated, but using 1.439 g of ammonium hydrogen difluoride in step 1) instead of the 2.877 g.
- Example 1 The amount of ammonium hydrogen difluoride used in Example 1 was selected to replace all the oxygen from the calcium oxide of the glass with fluoride ions.
- the lesser amounts in Examples 2 and 3 were (obviously) meant to achieve less than total replacement.
- the level of fluoride in the glass would have a bearing on the fluoride release from the resulting resin-modified cement, the reactivity of the glass in cement formation, and the strength of the resulting glass-ionomer cements. In these Examples, no temperature above 220C is required.
- Examples 4-7 The ground cement gel made according to Examples 1 to 3 can be used to make a single-paste composition or as a component in both pastes of a two-paste cement composition.
- the ground cement gel of Examples 1-3 is used as one component and the fluorinated glass being the 5 parts of powder referred to in step 5 of Example 1 is used as another component in a single-paste system having the composition shown in column 1.1.
- this composition (containing glass and aqueous poly)acrylic acid) intimately mixed) is non-setting and can be kept indefinitely in the dark.
- the fluoridated glass-depleted cement gel is for fluorine release during the life of the set cement
- the methacrylates are the resins and cross-linking monomers that polymerise via the application of light;
- the Quantacure chemicals and camphorquinone are the light-sensitive chemicals that are decomposed by the light source
- Aduvex and butylated hydroxy toluene are stabilisers in light-sensitive product compositions; • OX50 and NP-R711 are fumed silica products from Degussa Ltd;
- Raysorb T-3000 is a barium-containing aluminosilicate glass, employed in the cements to achieve enhanced radiopacity;
- P(VPA-AA) is the copolymer of vinyl phosphonic acid and acrylic acid. It is supplied by Albright & Wilson Ltd., and reacts with Z61 glass.
- Z61/3 cement precursor mixture is a zinc fluoride-containing anhydrous powder which re-introduces the glass ionomer reaction to the otherwise non-reacting paste 1.1. Its composition is 822 mg "oxide", 137 mg 35% aqueous solution of poly(acrylic acid) of chain length 75000 and 41 mg tartaric acid, the "oxide” itself being non-reactive with the poly(acrylic acid) and being the result of heat-treating at 1200°C for 1 hour a well-ground mixture of 127 parts zinc fluoride, 6 parts bentonite, 25.74 parts calcium fluoride, 1.34 parts Keltrol xanthan gum, 0.1 parts ⁇ ansa surfactant for assisting dissolution of the gum, 240 parts water and 2.8 parts zinc acetate; bentonite is an aluminosilicate being typically 43.8 parts silica, 9.1 parts alumina, 3.2 parts calcium oxide, 2.5 parts magnesium oxide, 0.9 parts ferric oxide and 1.5 parts sodium oxide.
- the other paste i.e. that shown in column 1.2 of Example 4, is a partially reacted cement which remains indefinitely stable, viscous and non-setting until exposed to light. It may be used as a single-paste light-curable lining cement, as a bonding agent, or directly as a restorative cement.
- Example 6
- Example 5 being a light-cured cement for the aesthetic restoration of anterior teeth classes III and V:
- Fumed silica Degussa RNP711 1.000 g Fluoridated glass-depleted cement (Example 2) 1.000 g (Example 6A: 1.5 g)
- Example 6 A The cement of Example 6 A was found to have the following properties :- Time for full light cure: 40 seconds
- Depth of light cure at and after 40 seconds 3.9 mm Depth of light cure at 20 seconds: 3.4 mm Compressive strength after 1 day: 220 MPa Diametral tensile strength after 1 day: 30 MPa Flexural strength after 1 day: 50 MPa Tensile bonding strength via Syntac (? type) adhesive after 1 day:
- the paste of Example 4 (“1.1") was mixed with the paste of Example 5 ( ⁇ 1.2 of Example 4). These pastes, when mixed, are light-curable.
- the differences between pastes 1.1 and 1.2, and the reason for the formation of an auto-set cement, is the presence of the Z61/3 zinc fluoride-based glasses (+poly(acrylic acid) PAA, tartaric acid and water) in paste 1.2, and the presence of poly(vinyl phosphonic/acrylic) acid P(VPA-AA) in paste 1.1
- the zinc fluoride-based glasses react with the P(VPA-AA) to form stable cements with definite working and setting times.
- paste 1.2 The zinc fluoride glass and poly(acrylic acid) present in paste 1.2 remain indefinitely in "suspended animation" as a partially-formed viscous, non-setting paste that is stable in the presence of the light cured resin systems, as long as the paste is sealed against evaporation and the pH is kept below about 3-4.
- paste 1.2 has radio-opaque inert fillers to enhance the radiopacity of the resulting cement. (Zinc fluoride is also radio-opaque.)
- Pastes 1.1 and 1.2 are similar in that they include in their compositions fluoride-containing preformed glass-ionomer cement. They may thus be considered to be complete glass-ionomer cements.
- the poly(vinylphosphonic) acid of paste 1.1 reacts with the "oxide" of Z61/3 of paste 1.2, to form a vinylphosphate ionomer.
- the peroxide and amine components of pastes 1.1 and 1.2 react to create free radicals, thereby affording a simultaneous three-mode cure, viz. chemical resin, light, and ionomer.
- the fluoride present in the ground cement can release slowly over a great length of time, inhibiting secondary caries at the restoration.
- compomers are an awkward combination of glass ionomer cement and composites, with inevitable compromises in performance, while this material, containing prereacted glass + acid, is a true glass ionomer cement.
- the material according to Example 7 is more colour-stable, and corrections for later colour-ageing do not have to be made; that is, the colour on initial setting will be broadly retained, leading to significantly greater patient satisfaction with the colour match both immediately and subsequently.
- Ca where present can be partially or wholly replaced by any one or more of Ba, Sr, La and other heavy divalent cations.
- Example 7 Unlike composites, which require the tooth to be acid-etched, the material of Example 7 will adhere to a tooth without damaging pretreatment of the tooth. Also unlike composites, the material of Example 7 does not contain the biologically undesirable monomer hydroxyethylmethacrylate - instead water is used.
- Example 8
- Examples 8 and 9 demonstrate the use of the particulate hydrogel according to the invention as an active filler in dental materials to impart fluoride-release (hence cariostatic) properties.
- Herculite Bayer
- dentally usable materials may be regarded as stemming from the novel light-curable paste as set forth above comprising a cross-linkable monomer, a light-activated initiator and a particulate material being the product of reaction set forth above, according to the scheme:
- Paste (a) + P(VPA-AA) or PNPA
- a paste can be (b)(i) + (c)(i)
- Another paste can be (b)(ii) + (c)(ii)
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Veterinary Medicine (AREA)
- Engineering & Computer Science (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Structural Engineering (AREA)
- Dental Preparations (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9704339 | 1997-03-03 | ||
GB9704339A GB2322860A (en) | 1997-03-03 | 1997-03-03 | Particulate material |
PCT/GB1998/000609 WO1998038967A1 (en) | 1997-03-03 | 1998-02-26 | Particulate hydrogel material |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0967956A1 true EP0967956A1 (de) | 2000-01-05 |
EP0967956B1 EP0967956B1 (de) | 2002-05-08 |
Family
ID=10808595
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98907070A Expired - Lifetime EP0967956B1 (de) | 1997-03-03 | 1998-02-26 | Teilcheförmiges hydrogelmaterial |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0967956B1 (de) |
JP (1) | JP2001513842A (de) |
DE (1) | DE69805291T2 (de) |
GB (1) | GB2322860A (de) |
WO (1) | WO1998038967A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6799636B2 (en) * | 2002-08-30 | 2004-10-05 | Halliburton Energy Services, Inc. | Methods and compositions for cementing in wellbores |
US10799429B2 (en) | 2016-02-25 | 2020-10-13 | 3M Innovative Properties Company | Kit of parts for producing a paste type glass ionomer cement, process of production and use thereof |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11228327A (ja) * | 1998-02-18 | 1999-08-24 | Gc Corp | 歯科用ペースト系グラスアイオノマーセメント組成物 |
GB2345697B (en) * | 1999-01-13 | 2003-01-08 | Gc Kk | Dental restorative material |
JP4467672B2 (ja) * | 1999-08-10 | 2010-05-26 | 株式会社ジーシー | 歯科用グラスアイオノマーセメントの硬化方法 |
US6793592B2 (en) | 2002-08-27 | 2004-09-21 | Acushnet Company | Golf balls comprising glass ionomers, or other hybrid organic/inorganic compositions |
EP1632211A1 (de) * | 2004-09-07 | 2006-03-08 | S & C Polymer Silicon- und Composite-Spezialitäten GmbH | Harzmodifzierter Dentalzement auf Polyalkenoatbasis |
AR048742A1 (es) * | 2004-12-22 | 2006-05-24 | Gador Sa | Sistema de aplicacion de medicamentos intra-oral |
ATE473723T1 (de) * | 2005-08-05 | 2010-07-15 | 3M Espe Ag | Dentalzusammensetzungen mit einem oberflächenmodifizierten füllstoff |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2929121A1 (de) * | 1979-07-18 | 1981-02-12 | Espe Pharm Praep | Calciumaluminiumfluorosilikatglas- pulver und seine verwendung |
GB9307777D0 (en) * | 1993-04-15 | 1993-06-02 | Shofu Inc | Dental cements |
-
1997
- 1997-03-03 GB GB9704339A patent/GB2322860A/en not_active Withdrawn
-
1998
- 1998-02-26 JP JP53826198A patent/JP2001513842A/ja active Pending
- 1998-02-26 WO PCT/GB1998/000609 patent/WO1998038967A1/en active IP Right Grant
- 1998-02-26 EP EP98907070A patent/EP0967956B1/de not_active Expired - Lifetime
- 1998-02-26 DE DE69805291T patent/DE69805291T2/de not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO9838967A1 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6799636B2 (en) * | 2002-08-30 | 2004-10-05 | Halliburton Energy Services, Inc. | Methods and compositions for cementing in wellbores |
US7238229B2 (en) | 2002-08-30 | 2007-07-03 | Halliburton Energy Services, Inc. | Methods and compositions for cementing in well bores |
US10799429B2 (en) | 2016-02-25 | 2020-10-13 | 3M Innovative Properties Company | Kit of parts for producing a paste type glass ionomer cement, process of production and use thereof |
Also Published As
Publication number | Publication date |
---|---|
DE69805291D1 (de) | 2002-06-13 |
EP0967956B1 (de) | 2002-05-08 |
DE69805291T2 (de) | 2002-12-05 |
WO1998038967A1 (en) | 1998-09-11 |
JP2001513842A (ja) | 2001-09-04 |
GB2322860A (en) | 1998-09-09 |
GB9704339D0 (en) | 1997-04-23 |
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